CN101563387A - Polyphenylenepolymethylene polyisocyanate and its use for producing polyurethane foams - Google Patents
Polyphenylenepolymethylene polyisocyanate and its use for producing polyurethane foams Download PDFInfo
- Publication number
- CN101563387A CN101563387A CNA200780042797XA CN200780042797A CN101563387A CN 101563387 A CN101563387 A CN 101563387A CN A200780042797X A CNA200780042797X A CN A200780042797XA CN 200780042797 A CN200780042797 A CN 200780042797A CN 101563387 A CN101563387 A CN 101563387A
- Authority
- CN
- China
- Prior art keywords
- polyphenylene polymethylene
- polymethylene polyisocyanates
- weight
- polyisocyanates
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 105
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 105
- 229920005830 Polyurethane Foam Polymers 0.000 title claims description 28
- 239000011496 polyurethane foam Substances 0.000 title claims description 28
- -1 polyphenylene Polymers 0.000 claims description 185
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 83
- 239000006260 foam Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 7
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 229920000582 polyisocyanurate Polymers 0.000 claims description 2
- 239000011495 polyisocyanurate Substances 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 38
- 239000000203 mixture Substances 0.000 description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 19
- 229920005862 polyol Polymers 0.000 description 17
- 150000003077 polyols Chemical class 0.000 description 17
- 229920000570 polyether Polymers 0.000 description 15
- 239000004721 Polyphenylene oxide Substances 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000000443 aerosol Substances 0.000 description 12
- 239000012948 isocyanate Substances 0.000 description 11
- 150000002513 isocyanates Chemical class 0.000 description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 10
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008602 contraction Effects 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 229930000044 secondary metabolite Natural products 0.000 description 6
- 239000001294 propane Substances 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 4
- SFNALCNOMXIBKG-UHFFFAOYSA-N ethylene glycol monododecyl ether Chemical compound CCCCCCCCCCCCOCCO SFNALCNOMXIBKG-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- 230000008646 thermal stress Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 2
- LOOCNDFTHKSTFY-UHFFFAOYSA-N 1,1,2-trichloropropyl dihydrogen phosphate Chemical compound CC(Cl)C(Cl)(Cl)OP(O)(O)=O LOOCNDFTHKSTFY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- OHKOAJUTRVTYSW-UHFFFAOYSA-N 2-[(2-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC=C1CC1=CC=CC=C1N OHKOAJUTRVTYSW-UHFFFAOYSA-N 0.000 description 1
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical compound FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 description 1
- ZMSQJSMSLXVTKN-UHFFFAOYSA-N 4-[2-(2-morpholin-4-ylethoxy)ethyl]morpholine Chemical compound C1COCCN1CCOCCN1CCOCC1 ZMSQJSMSLXVTKN-UHFFFAOYSA-N 0.000 description 1
- PWZCWMZJLQNYPL-UHFFFAOYSA-N C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.CCCCCCCCCC Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.CCCCCCCCCC PWZCWMZJLQNYPL-UHFFFAOYSA-N 0.000 description 1
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920005863 Lupranol® Polymers 0.000 description 1
- 229920005869 Lupranol® 1200 Polymers 0.000 description 1
- 229920005899 Lupranol® 3423 Polymers 0.000 description 1
- 229920005900 Lupranol® 3424 Polymers 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011093 chipboard Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 150000001983 dialkylethers Chemical class 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexamethylene diamine Natural products NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- 239000005436 troposphere Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
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- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
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- C08G18/4252—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups derived from polyols containing at least one ether group and polycarboxylic acids derived from polyols containing polyether groups and polycarboxylic acids
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- C08G18/40—High-molecular-weight compounds
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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Abstract
The invention relates to polyphenylenepolymethylene polyisocyanates (B) comprising (B1) the 2-ring product of polyphenylenepolymethylene polyisocyanate (B2) the 3-ring product of polyphenylenepolymethylene polyisocyanate (B3) the 4-ring product of polyphenylenepolymethylene polyisocyanate (B4) the 5-ring product of polyphenylenepolymethylene polyisocyanate, wherein the constituents (B2), (B3) and (B4) are, at a content of (B1) up to 55% by weight, based on the weight of (B), present in a weight ratio of (B2) : (B3) : (B4) of 8 +- 4 : 3.5 +- 1.8 : 1.2 +- 0.9 and the component (B) comprises at least 85% by weight, based on the weight of the component (B), of the constituents (B1), (B2), (B3) and (B4).
Description
The invention provides polyphenylene polymethylene polyisocyanates (MDI), its preparation method and the purposes in preparation urethane, especially polyurethane foam thereof with specific composition.
For a long time with regard to known polyurethane foam, and repeatedly it is described.Polyurethane foam can be used for many industrial application.It is generally by making polyisocyanates and having at least two to the respond compound prepared in reaction of active hydrogen atom of isocyanate groups.
Two kinds of polyurethane foams commonly used are hard polyurethane foams and the monocomponent bubble that also is known as aerosol foam.
Hard polyurethane foams mainly is used for heat insulation in refrigeration equipment for example, transportation equipment or building, also is used to prepare structural member, especially sandwich component.
The polyisocyanates that is used to prepare above-mentioned urethane is generally aromatic polyisocyanate, is specially MDI and higher homologue thereof.
Monocomponent bubble from aerosol container is an installing material, is usually used in installing in buildings window and door in construction industry, also as packing material, is used for cavity that is produced by building or the hole that passes wall that is used for pipelining.This type of aerosol container comprises prepolymer and whipping agent and additive.By utilizing the content in the whipping agent jetting container to form required foam, so by bubble foaming with by contacting the moisture-curable in the atmosphere.Known monocomponent bubble based on the prepolymer that contains NCO is preferably a kind of in this foam.Exist and produce the multiple product of rigid foam to flexible foam, this depends on the composition of described product.
The important requirement that polyurethane foam must satisfy is a dimensional stability.Dimensional stability refers to can not change its volume behind the foam curing, especially can not shrink.With regard to rigid foam, contraction can produce hole in foam, and causes it to break away from from tectum.
With regard to the monocomponent bubble that is used to install window and door, the stability that contraction can cause having installed door and window is not enough.
The dimensional stability problem, especially the dimensional stability problem of monocomponent bubble, be not solved yet industrial, therefore, with regard to present known grade, as technical inevitable shrinkage value, during use in 5% contraction and the torrid zone at the most in the room-temperature applications under 40 ℃ and 90% relative humidity at the most 10% contraction be still permission.
With regard to the two-pack foam, especially with regard to the two-pack rigid foam, the contraction problem especially is present in the largest part, and does not have any guide of this issue-resolution.
In addition, market day by day demand have light color foam.The foam of the polyphenylene polymethylene polyisocyanates preparation that the utilization that is provided at present is commonly used is generally brown.May think that this is unsatisfactory, foam is in the application that can see especially therein.
Therefore the object of the invention is to provide the polyurethane foam with excellent machinability and use properties, especially good dimensional stability.In addition, the light foamy market requirement should obtain solving.Described method should allow to prepare the foam that is used for various application, especially single component and now make foam and hard polyurethane foams.
Beat allly be, can be by in the foamy preparation process, diphenylmethanediisocyanate and mixture with polyphenylene polymethylene polyisocyanates of specific composition being realized this purpose as isocyanate component.
Correspondingly, the invention provides polyphenylene polymethylene polyisocyanates (B), it comprises:
(B1) 2 of polyphenylene polymethylene polyisocyanates ring products
(B2) 3 of polyphenylene polymethylene polyisocyanates ring products
(B3) 4 of polyphenylene polymethylene polyisocyanates ring products
(B4) 5 of polyphenylene polymethylene polyisocyanates ring products
Be under the prerequisite of 55 weight % at the most based on the weight of (B) wherein at the content of (B1), component (B2), (B3) and (B4) with (B2): (B3): (B4)=8 ± 4: 3.5 ± 1.8: 1.2 ± 0.9 weight ratio exists, and component (B) comprises at least 85 weight % components (B1), (B2), (B3) and (B4) based on the weight of component (B).
The present invention also provides by making (A) have two to isocyanate groups the respond compound (hereinafter being also referred to as polyol component) of active hydrogen atom and (B) method of polyisocyanates prepared in reaction polyurethane foam at least, wherein with polyphenylene polymethylene polyisocyanates of the present invention as polyisocyanates (B).
The present invention also provides the method for preparing polyphenylene polymethylene polyisocyanates of the present invention, and described method comprises the steps:
A) by making polyphenylene multi-methylene polyamine and phosgene reaction prepare polyphenylene polymethylene polyisocyanates,
B) by product in the polyphenylene polymethylene polyisocyanates of removal step a).
Except that component (B1)-(B4), polyphenylene polymethylene polyisocyanates of the present invention also has other components.Therefore, polyphenylene polymethylene polyisocyanates of the present invention (B) also comprises the polyphenylene polymethylene polyisocyanates with 6 or more a plurality of rings.For this reason, term " ring " refers to aromatic ring.Hereinafter also the compound that comprises two above aromatic rings can be called higher homologue.
Polyphenylene polymethylene polyisocyanates of the present invention (B) also can comprise other compounds with isocyanate groups, the mutual reaction product of isocyanic ester for example, be specially diazacyclo butanone imines (uretonimine), and/or have the polyphenylene polymethylene polyisocyanates of 6 or more a plurality of rings.
The ratio of these type of other components of preferred ingredient (B) is based on the no more than 15 weight % of the weight of component (B).
Preferred polyphenylene polymethylene polyisocyanates (B) comprises no more than 11 weight % based on the weight of (B) in all cases, preferred especially no more than 6 weight %, concrete no more than 3 weight % diazacyclo butanone imines.Its weight that is based on (B) is the part of 15 other compounds of weight %.
Generally determine to have the content of the polyphenylene polymethylene polyisocyanates of different rings quantity by gas chromatogram.Analyze the content of determining diazacyclo butanone imines in the polyphenylene polymethylene polyisocyanates based on the correction (testing method PFO/A 00/22-03) that utilizes 3 ring diazacyclo butanone imines by FT-IR.
The content of the free NCO end group of preferred polyphenylene polymethylene polyisocyanates of the present invention is 31.0-33.3 weight %.
Preferably the iodine color value that records according to DIN 6162 and DIN 6164 of the polyphenylene polymethylene polyisocyanates of the present invention (B) by the extraction gained is less than 5 iodine, L
*Value is greater than 96, b
*Value is less than 15.
Polyphenylene polymethylene polyisocyanates of the present invention can prepare by traditional method.These methods are normally known, and comprise that acid catalyzed reaction by aniline and formaldehyde prepares ditan diamines (MDA) and if higher homologue, neutralization and aftertreatment thus gained amine mixt, make the latter and phosgene reaction generate polyphenylene polymethylene polyisocyanates, purification, aftertreatment and suitable part to remove 2 ring MDI.Unexpectedly taken place owing to forming the destruction that by product causes polyphenylene polymethylene polyisocyanates, particularly, taken place to remove the 2 caused destructions of encircling in the product processes of thermal stresses to polyphenylene polymethylene polyisocyanates by aftertreatment polyphenylene polymethylene polyisocyanates and distillation.If the time that thermal stresses exists is very short, for example when less separation amount 2 ring MDI, then can avoid these shortcomings.In addition, importantly the temperature in the described process is not increased to more than 220 ℃.The iodine color value that the polyphenylene polymethylene polyisocyanates of the present invention (B) of preferred preparation thus records according to DIN 6162 and DIN 6164 is less than 10 iodine, L
*Value is greater than 89, b
*Value is less than 30.
Prepare polyphenylene polymethylene polyisocyanates of the present invention with following preferred method: at first polyphenylene multi-methylene polyamine and phosgene are reacted with conventional and known way, at processing step b subsequently at processing step) in product is separated with by product such as diazacyclo butanone imines.If they generate same products, then other operational paths also can in principle.
Processing step generally is known a), and comprise as mentioned above aniline and formaldehyde acid catalyzed reaction, polyamines that neutralization and aftertreatment generated, make the latter and phosgene reaction generate the described polyisocyanates of corresponding polyisocyanates and aftertreatment and purification.As mentioned above, polyphenylene polymethylene polyisocyanates of the present invention is separated with secondary compound such as diazacyclo butanone imines.In preparation and aftertreatment, generate these secondary compound, especially polyisocyanates under the thermal stresses effect.Initial polyisocyanates comprise at most 25 weight % these from the secondary compound in the preparation process, for example diazacyclo dimethyl diketone (uretdione), diazacyclo butanone imines and urea chloride.Preferably remove these secondary compounds by the liquid-liquid extraction of using polarity or non-polar solvent.In a preferred embodiment, preferred hydrocarbons such as hexanaphthene are solvent.For example DE 1,543,258 or EP 133 538 this class methods have been described.
In a preferred embodiment of step b), make employed polyphenylene polymethylene polyisocyanates and hexanaphthene with isocyanic ester: solvent=1: 1-1: 15, preferred 1: 1.5-1: 12, preferred especially 1: 2.5-1: 10 ratio is at 20-90 ℃, contact is 1-180 minute under preferred 30-80 ℃ the temperature, preferred 5-150 minute.At 20-40 ℃, leave standstill product mixtures under the preferred room temperature then, be separated until finishing.Lower floor is mutually for comprising diazacyclo butanone imines that falls to be separated and " raffinate " that encircles more MDI homologue.The upper strata is mutually for comprising the low polyphenylene polymethylene polyisocyanates of required diazacyclo butanone imines content and " extract " of solvent.Separate two-phase, for example remove solvent substantially fully by vacuum distilling.The content of preferred residual hexanaphthene is less than 20ppm.
Preferably the iodine color value that records according to DIN 6162 and DIN 6164 of the polyphenylene polymethylene polyisocyanates of the present invention (B) that obtains by extraction is less than 5 iodine, L
*Value is greater than 96, b
*Value is less than 15.
When in preparation process, making the thermal stresses that acts on the polyphenylene polymethylene polyisocyanates keep lower and carrying out the extraction of polyphenylene polymethylene polyisocyanates again, obtain good especially result.
Also can the polyphenylene polymethylene polyisocyanates batch of material that does not have the present invention's composition be extracted.At this moment, the content of secondary compound can be reduced to content of the present invention more than 15 weight %.In addition, can encircle less product thus is that direction changes the ring distribution.Also can after removing 2 ring MDI, part carry out the extraction of polyphenylene polymethylene polyisocyanates, because remove the increase that secondary compounds content can take place in the 2 ring MDI processes usually.
Preferably the content of 2 of the polyphenylene polymethylene polyisocyanates of the present invention (B) by aforesaid method feature gained ring products (B1) is 20-50 weight % based on the weight of (B) in polyphenylene polymethylene polyisocyanates preparation process, component (B2), (B3) and (B4) with (B2): (B3): (B4)=8 ± 4: 3.5 ± 1.8: 1.2 ± 0.9 weight ratio exists, and component (B) comprises at least 85 weight % components (B1), (B2), (B3) and (B4) based on the weight of component (B).
When obtaining polyphenylene polymethylene polyisocyanates of the present invention (B) by extraction, the content of preferred 2 ring products (B1) is 20-55 weight % based on the weight of (B), component (B2), (B3) and (B4) with (B2): (B3): (B4)=8 ± 4: 3.5 ± 1.8: 1.2 ± 0.9 weight ratio exists, and component (B) comprises at least 85 weight % components (B1), (B2), (B3) and (B4) based on the weight of component (B).
When removing 2 ring MDI by part and extraction obtains polyphenylene polymethylene polyisocyanates of the present invention (B) subsequently, the content of preferred 2 ring products (B1) is 2-20 weight % based on the weight of (B), component (B2), (B3) and (B4) with (B2): (B3): (B4)=8 ± 4: 3.5 ± 1.8: 1.2 ± 0.9 weight ratio exists, and component (B) comprises at least 85 weight % components (B1), (B2), (B3) and (B4) based on the weight of component (B).
Polyphenylene polymethylene polyisocyanates of the present invention can be used to prepare polyurethane foam as mentioned above.The present invention preferably is applied as one-component polyurethane foam and hard polyurethane foams.For this reason, make polyphenylene polymethylene polyisocyanates of the present invention (B) and have at least two respond compound (A) reaction of active hydrogen atom of isocyanate groups.
In the preparation of one-component polyurethane foam, in the presence of whipping agent,, carry out isocyanate component (B) in the preferred aerosol canister and have at least two the respond reaction of compound (A) of active hydrogen atom of isocyanate groups at pressurized vessel., the polyol component (A) and the isocyanate component (B) of ratio mentioned above are introduced in the pressurized vessel with whipping agent for this reason, thereby in pressurized vessel, generated the lower prepolymer of the present invention of free isocyanate groups mass contg.Being used to prepare single component now makes foamy whipping agent commonly used and is for example R134a (Tetrafluoroethane), R152a (1, the 1-C2H4F2 C2H4F2), dme, propane, normal butane and Trimethylmethane, the mixture of preferably propane, normal butane and Trimethylmethane.
The NCO content that preferably is present in the prepolymer in the aerosol canister is about 5-28 weight %, preferred 8-24 weight %, preferred especially 9-18 weight %.The prepolymer that NCO content is lower produces softer aerosol foam, and the higher prepolymer of NCO content then correspondingly produces harder foam.
For using described one-component polyurethane foam, reduce the pressure of pressurized vessel.At this moment, the prepolymer of ejection foams by the forming process of whipping agent, and by the moisture-curable in the contact atmosphere.
For many application of one-component polyurethane foam, need to add fire retardant as additive, they have the effect that reduces viscosity equally.Only need add the fire retardant that reaches finished foam burning grade institute necessary amounts.
Generally trialkylphosphate and phosphoric acid trichlorine alkyl ester are used as the fire retardant that adds.Preferred alkyl has 1-4, preferred especially 1-3 carbon atom.Particularly preferred compound is trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate chloromethyl ester, Trichloroethyl Phosphate and trichloropropyl phosphate.Can use these compounds separately or with mutual any mixture.
The add-on of fire retardant depends on the required satisfied requirement of foam.For the prescription of fireproof one-component polyurethane foam, the fire retardant total content that adds in the NCO prepolymer that exists in jar is necessary for about 8-18 weight % based on the weight of prepolymer, preferred 12-16 weight %.Content is on the low side, and flameproof protection may be not enough, and the flame retardant agent content height that adds, foam flows, and promptly it can not be applied to vertical surface, and perhaps a large amount of fire retardants move out from foam.
In the preparation of rigid foam of the present invention, as is generally known, isocyanate component with have at least two the respond compound (A) of active hydrogen atom of isocyanate groups reacted in the presence of catalyzer and whipping agent, wherein polyphenylene polymethylene polyisocyanates of the present invention (B) is used for the inventive method.
Can will eliminate the water of carbonic acid gas as whipping agent with the isocyanate groups reaction.Also can be used in combination pneumatogen, or replace water with pneumatogen with water.These are that starting ingredient is inertia, the compound that room temperature is generally liquid and evaporates under the urethane reaction condition.The boiling point of preferred these compounds is lower than 50 ℃.Pneumatogen comprises that also room temperature is gas and introduces in the starting ingredient or be dissolved in wherein compound adding to depress, for example carbonic acid gas, lower boiling paraffinic hydrocarbons and fluoro paraffinic hydrocarbons.
Described compound generally is selected from paraffinic hydrocarbons and/or naphthenic hydrocarbon, dialkyl ether, ester, ketone, acetal with at least 4 carbon atoms, have the fluoro paraffinic hydrocarbons of 1-8 carbon atom and have the tetraalkyl silane of 1-3 carbon atom in alkyl chain, is specially tetramethylsilane.
The example that can mention is a propane, normal butane, Trimethylmethane and tetramethylene, Skellysolve A, iso-pentane and pentamethylene, hexanaphthene, dme, methyl ethyl ether, methyl butyl ether, methyl-formiate, acetone and in the troposphere degraded and the fluoro paraffinic hydrocarbons that therefore can not damage the ozone layer, for example trifluoromethane, methylene fluoride, 1,1,1,3,3-3-pentafluorobutane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2-Tetrafluoroethane, C2H4F2 C2H4F2 and heptafluoro-propane.Especially preferably use pentamethylene and/or Skellysolve A.Can use described pneumatogen separately or with mutual arbitrary combination.
Be the preparation hard polyurethane foams, make polyol component (A) and polyisocyanates (B) so that isocyanate index is 100-220, the quantitative response of preferred 125-195.
Can prepare hard polyurethane foams in batches or continuously by known mixing device.
Generally be equipped with hard PUR foam of the present invention by the two-pack legal system.In the method, make to have at least two the respond compound (A) of active hydrogen atom of isocyanate groups mixed with fire retardant, whipping agent, catalyzer and other auxiliary agents and/or additive and form polyol component, if the mixture of polyol component and polyisocyanates or polyisocyanates and suitable flame retardant and whipping agent (being also referred to as isocyanate component) reacts.
Be 15-35 ℃ in temperature generally, preferred 20-30 ℃ is mixed starting ingredient down.Can utilize high pressure or low-temperature measurement machine that reaction mixture is introduced in the supporting tool of sealing.For example prepare sandwich component by this method in batches.
Utilize the foam of the inventive method preparation unexpectedly to have very shallow color, sometimes or even white.Described foam size is stable, and can very well use.
Other polyvalent alcohols as for being used to prepare polyurethane foam of the present invention can provide following details:
Can be used for the present invention prepares rigid foam and preparation and is used for single component and now makes having at least two the respond compound (A) of active hydrogen atom of isocyanic ester being specially Aethoxy Sklerol and/or the polyesterols that OH value is 100-1200mg KOH/g of foamy prepolymer process.
Generally by having 2-12 carbon atom, the polyfunctional alcohol of preferred 2-6 carbon atom, preferred dibasic alcohol and the polyfunctional carboxylic acids with 2-12 carbon atom (for example Succinic Acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, decane dioctyl phthalate, toxilic acid and fumaric acid, the preferably naphthalic acid of phthalic acid, m-phthalic acid, terephthalic acid and isomery) the employed polyesterols of condensation prepared.
The functionality of employed Aethoxy Sklerol is generally 2-8, is specially 3-8.
Particularly, use polyether glycol, for example the polyether glycol for preparing by the cationoid polymerisation of oxirane in the presence of catalyzer (preferred alkali metal hydroxide) by the currently known methods preparation.
Generally with oxyethane and/or propylene oxide, preferred pure 1,2 epoxy prapane is as oxirane.
Employed starter molecules is specially has at least 3 in the molecule, the compound of preferred 4-8 hydroxyl or at least two primary aminos.
Preferably the Mannich condenses with TriMethylolPropane(TMP), glycerine, tetramethylolmethane, sugar compounds (for example glucose, sorbyl alcohol, mannitol and sucrose), polyhydroxy phenol, resole (for example oligomeric condensation product of phenol and formaldehyde) and phenol, formaldehyde, two alkanolamines and trimeric cyanamide has at least 3 as in the molecule, the starter molecules of preferred 4-8 hydroxyl.
Preferably with aromatic diamine and/or polyamines (phenylenediamine for example, 2,3-, 2,4-, 3,4-and 2,6-tolylene diamine and 4,4 '-, 2,4 '-and 2,2 '-diaminodiphenyl-methane) and aliphatic diamine and polyamines (for example quadrol) as the starter molecules that has at least two primary aminos in the molecule.
The functionality of preferred, polyethers polyvalent alcohol is 3-8, and preferred hydroxyl value is 100-1200mg KOH/g, is specially 240-570mg KOH/g.Also can use hydroxyl value less than 100mg KOH/g and functionality polyvalent alcohol, especially Aethoxy Sklerol as 2-3.Can adjust foamy character thus, for example now making under the foamy situation with high flexible more in single component is direction.
Have at least two the respond compound (A) of active hydrogen atom of isocyanic ester also comprised the chain extension agent and the linking agent that can use simultaneously.If provable adding difunctional chain extenders, trifunctional and more multifunctional linking agent or suitable its mixture help changing mechanical property.Preferably with alkanolamine and especially molecular weight less than 400, be preferably the dibasic alcohol of 60-300 and/or trivalent alcohol as chain extension agent and/or linking agent.
Advantageously, the consumption of chain extension agent, linking agent or its mixture is 1-20 weight % based on polyol component (A), preferred 2-5 weight %.
Except that the pure and mild polyether glycol of described polyester polyols, chain extension agent and linking agent, also can be with monohydroxy-alcohol as other OH functional compounds, described OH functional compound is used for regulating molecular weight in the preparation process of the required polyol component in one-component polyurethane foam field (A) as directed reagent, with foam surface layer and the final stability in storage that improves that forms transmissibility.If desired, (the OH value: the consumption of monohydroxy-alcohol about 40mg KOH/g) is generally 10 weight % at the most based on polyol component (A) to these molecular weight for 1400g/mol at the most.
Other information of employed Aethoxy Sklerol and polyesterols and preparation thereof be Kunststoffhandbuch for example as seen, the 7th volume " urethane ", and G ü nter Oertel compiles, Carl-Hanser-Verlag, Munich, the 3rd edition, 1993.
In a particularly preferred embodiment of preparation one-component polyurethane foam, with the mixture of following component as polyol component (A):
(A1) to be not more than the polyester polyols of 600g/mol pure and mild for molecular weight
(A2) molecular-weight average is polyether glycol or the polyether glycol mixture of 1000-5000g/mol.
Preferably will be used as polyester polyol (A1) based on the polyester polyol of Tetra hydro Phthalic anhydride/glycol ether/polyoxyethylene glycol.
Preferably with polyester polyol (A1): polyether glycol or polyether glycol mixture (A2)=1: 6-3: 1 weight ratio is used polyvalent alcohol (A1) and (A2).
Employed catalyzer is specially the compound of reaction that quickens isocyanate groups and active group that isocyanate groups is responded greatly.This type of catalyzer is a strong basicity amine, for example aliphatic secondary amine, imidazoles, amidine class and alkanolamine.
If isocyanurate group is attached in the rigid foam, then need special catalyst.Generally, be specially potassium acetate and solution thereof as isocyanurate catalyst with metal carboxylate.In the preparation process of this class A foam A (being also referred to as urethane-polyisocyanurate foam), generally the index with 160-450 carries out component (A) and reaction (B).
Set forth the present invention by following examples.
Embodiment 1-(monocomponent bubble)
1.1 the preparation of polyol component:
By mixing 300g is the polyester polyol of 470g/mol based on Tetra hydro Phthalic anhydride/glycol ether/polyoxyethylene glycol and molecular weight, 208g is the polyether glycol of 4000g/mol based on glycerine/propylene oxide/oxyethane and molecular weight, 30g is the polyether glycol of 540g/mol based on sucrose/pentanediol/glycol ether and molecular-weight average, the 40g molecular weight is the polyoxyethylene glycol of 600g/mol, the 59g molecular weight is the simple function of the 500g/mol polyoxyethylene glycol that methylates, the 25g suds-stabilizing agent, the 330g trichloropropyl phosphate, 8g two (morpholino ethyl) ether and 0.5g silicone oil prepare polyol component.
1.2 the preparation of isocyanic ester preparation:
As described below utilize hexanaphthene with single step extraction process extraction monomer M DI content be 37%, NCO content is 31.2% weight, viscosity 25 ℃ the time is that 213mpas, colour are 20 iodine, L
*Value is 85.6, b
*Value be 70.1 and diazacyclo butanone imines content be 8.4% weight polyphenylene polymethylene polyisocyanates (trade(brand)name:
M20).
Make polyphenylene polymethylene polyisocyanates and hexanaphthene with isocyanic ester: the ratio of solvent=1: 3 contacts 60 minutes under 50 ℃.Room temperature leaves standstill product mixtures and is separated until finishing then.
The upper strata is mutually for comprising " extract " of required polyphenylene polymethylene polyisocyanates and solvent.Thoroughly remove solvent (content of residual hexanaphthene is less than 20ppm) in the extract by vacuum distilling.
Obtain product thus, can the described product of following sign:
Viscosity: 50mPas (25 ℃)
NCO content: 32.6 weight %
Monomer (B1) content: 49.1 weight %
Diazacyclo butanone imines content: 1.6 weight %
Colour: 0.8 iodine
L
*Value: 99.3
b
*Value: 5.1
The content of the higher homologue of diphenylmethanediisocyanate and ratio:
(B2) 3 of polyphenylene polymethylene polyisocyanates ring products: 30.4 weight %
(B3) 4 of polyphenylene polymethylene polyisocyanates ring products: 11.4 weight %
(B4) 5 of polyphenylene polymethylene polyisocyanates ring products: 4.2 weight %
Obtain component (B1): (B2): (B3)=7.2: 2.7: 1 ratio.
The product usefulness that will prepare as mentioned above with this kind form acts on the isocyanate component that following single component is now made foam preparation.
1.3 the single component of light color and dimensional stabilizing is now made the foamy preparation
The polyol component of 268g embodiment 1.1 is introduced in 1 liter of aerosol canister.After adding the isocyanic ester preparation of 361g embodiment 1.2, can be suitable for the device sealing aerosol canister of aerosol canister prepared in laboratory by oblique valve utilization.
Follow propane/butane mix and the 94g tetrafluoromethane (R134a) formed by 20 weight % propane and 80 weight % butane by valve introducing 56g dme, 38g, by jolting homogenize content.
Realize temper(ing) by the aerosol canister of preserving preparation thus 50 ℃ of insulations, thereby after can and being cooled to room temperature preservation 24 hours the aerosol canister of preparation is tested.
For this reason, a wetting thieving paper that is placed on the planarizing substrate, the foam pipe that utilization screws on is opened the content of valve with foaming mixtures ejection aerosol canister that incline.
With strips ejection foam, use water-wet with the foam surface between the foam strips of layer form ejection.
The solidified foam is tested to measure its performance (seeing Table 1.4).
1.4 single component is now made the foamy performance
| Embodiment 1 described foam | With commercially available foam contrast | |
| Color | White | Huang/brown |
| Tensile strength | 24.1N/cm 2 | 8N/cm 2 |
| Extension at break | 21％ | 20％， |
| Compression stress (10% distortion) | 5N/cm 2 | 5N/cm 2 |
| Dimensional stability ＊ | Do not shrink | -4.2％ |
Dimensional stability
*
Measurement is by two chipboards and spacer rod and introduce therebetween and the dimensional stability of the given the test agent made of solidified foam therein.Foam curing and remove spacer rod after, the spatial variations rate is as the tolerance of dimensional stability between assay plate.
Embodiment 2-(two-pack hard PUR foam)
2.1 the preparation of polyol component
By 377g Lupranol 3424 (based on sucrose, tetramethylolmethane, the polyether glycol of glycol ether and propylene oxide, the OH value is 403mg KOH/g), 230g Lupranol 3423 is (based on sucrose, the polyether glycol of glycerine and propylene oxide, the OH value is 490mg KOH/g), 20g glycerine, 300gLupranol 1100 is (based on the polyether glycol of propylene glycol and propylene oxide, the OH value is 104mgKOH/g), 54g Lupranol VP9319 (based on the polyether glycol of TriMethylolPropane(TMP) and propylene oxide, the OH value is 160mg KOH/g), 10g stabilizer T egostab B8443,5g stablizer NiaxSilicone SR 393 and 4.5g water prepare polyol blends.Add 34g catalyst mixture (23.3%N to this mixture, N-dimethylcyclohexylamine, 18.7%1-Methylimidazole, 28% 4-methyl hexamethylene diamine and 30%Lupranol 1200[are based on the polyether glycol of propylene glycol and propylene oxide, the OH value is 248mg KOH/g]) and the aqueous mixture (comprising 9% glycerine and 31% dipropylene glycol) of 50g glycerine/glycol, and by its preparation polyol component.
2.2 isocyanate component
Use embodiment 1.2 described isocyanate components.
2.3 process described component with preparation hard PUR foam
With polyol component: the ratio of mixture mix embodiment 2.1 and the 2.2 described components of isocyanate component=100: 136, foaming and solidify the back and obtain white rigid foam.Described foam (foam free) has following performance:
Time opening: 15 seconds
Set time: 48 seconds
Work the time of sending out: 85 seconds
Foam density: 37.2kg/m
3
Ultimate compression strength: 28.1N/cm
2
2.4 the contrast of dimensional stability
Use have be similar to the polyol component that embodiment 2.1 forms and for example at first use be similar to the isocyanate component of embodiment 1.2 described compositions and then use commercially available polyphenylene polymethylene polyisocyanates (trade(brand)name:
M20) preparation rigid foam sandwich plate solidifies the back and measures its contraction.
*Technical intelligence on the Elastopor H 1101/1/0
Claims (22)
1. a polyphenylene polymethylene polyisocyanates (B), it comprises:
(B1) 2 of polyphenylene polymethylene polyisocyanates ring products
(B2) 3 of polyphenylene polymethylene polyisocyanates ring products
(B3) 4 of polyphenylene polymethylene polyisocyanates ring products
(B4) 5 of polyphenylene polymethylene polyisocyanates ring products
Be under the prerequisite of 55 weight % at the most based on the weight of (B) wherein at the content of (B1), component (B2), (B3) and (B4) with (B2): (B3): (B4)=8 ± 4: 3.5 ± 1.8: 1.2 ± 0.9 weight ratio exists, and component (B) comprises at least 85 weight % components (B1), (B2), (B3) and (B4) based on the weight of component (B).
2. the polyphenylene polymethylene polyisocyanates of claim 1, wherein component (B) comprises at least 2 weight % components (B1) based on the weight of (B).
3. the polyphenylene polymethylene polyisocyanates of claim 1, wherein component (B) comprises other compounds that no more than 15 weight % have the polyphenylene polymethylene polyisocyanates of at least 6 rings and comprise isocyanate groups based on the weight of component (B).
4. the polyphenylene polymethylene polyisocyanates of claim 3, other compounds that wherein comprise isocyanate groups comprise diazacyclo butanone imines.
5. the polyphenylene polymethylene polyisocyanates of claim 3, other compound-bases that wherein comprise isocyanate groups comprise no more than 11 weight % diazacyclo butanone imines in the weight of polyphenylene polymethylene polyisocyanates (B).
6. the polyphenylene polymethylene polyisocyanates of claim 3, other compound-bases that wherein comprise isocyanate groups comprise no more than 6 weight % diazacyclo butanone imines in the weight of polyphenylene polymethylene polyisocyanates (B).
7. the polyphenylene polymethylene polyisocyanates of claim 3, other compound-bases that wherein comprise isocyanate groups comprise no more than 3 weight % diazacyclo butanone imines in the weight of polyphenylene polymethylene polyisocyanates (B).
8. the polyphenylene polymethylene polyisocyanates of claim 1, wherein the content of the free NCO end group of polyphenylene polymethylene polyisocyanates is 31.0-33.3 weight %.
9. one kind by making (A) have at least two to isocyanate groups the respond compound of active hydrogen atom and (B) method of polyisocyanates prepared in reaction polyurethane foam, wherein with the polyphenylene polymethylene polyisocyanates of claim 1 as polyisocyanates (B).
10. the method for claim 9 wherein is reflected under the whipping agent existence and carries out.
11. the method for claim 9 wherein is reflected under the catalyzer existence and carries out.
12. one kind by mixing (A) thus have at least two to isocyanate groups respond the compound of active hydrogen atom and (B) polyisocyanates make component (A) with (B) in the presence of whipping agent in pressurized vessel the method for prepared in reaction one-component polyurethane foam, wherein the polyphenylene polymethylene polyisocyanates with claim 1 is used as polyisocyanates (B).
13. the method for claim 12, wherein in component (A) and (B) reaction the consumption of component (B) to learn calculating excessive for tripling at least.
14. one kind by making (A) have at least two to isocyanate groups the respond compound of active hydrogen atom and (B) method of polyisocyanates prepared in reaction hard polyurethane foams in the presence of whipping agent, wherein the polyphenylene polymethylene polyisocyanates with claim 1 is used as polyisocyanates (B).
15. the method for claim 14, wherein the index with 100-220 carries out component (A) and reaction (B).
16. the method for claim 14 wherein utilizes the two-pack method to react.
17. one kind by making (A) have at least two to isocyanate groups the respond compound of active hydrogen atom and (B) method of polyisocyanates prepared in reaction hard polyaminoester-polyisocyanurate foam in the presence of whipping agent and catalyst for trimerization, wherein the polyphenylene polymethylene polyisocyanates with claim 1 is used as polyisocyanates (B).
18. the method for claim 17, wherein the index with 160-450 carries out component (A) and reaction (B).
19. a method for preparing the polyphenylene polymethylene polyisocyanates of claim 1, described method comprises the steps:
A) by making polyphenylene multi-methylene polyamine and phosgene reaction prepare polyphenylene polymethylene polyisocyanates,
B) by product in the polyphenylene polymethylene polyisocyanates of removal step a).
20. the method for claim 19, wherein step b) is extraction.
21. one kind by making polyphenylene multi-methylene polyamine and phosgene reaction prepare the method for the polyphenylene polymethylene polyisocyanates of claim 1, wherein temperature is no more than 220 ℃ in preparation and the aftertreatment polyphenylene polymethylene polyisocyanates process.
22. the purposes of the polyphenylene polymethylene polyisocyanates of claim 1 in the preparation polyurethane foam.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP06124306 | 2006-11-17 | ||
| EP06124306.9 | 2006-11-17 | ||
| PCT/EP2007/062188 WO2008058920A1 (en) | 2006-11-17 | 2007-11-12 | Polyphenylenepolymethylene polyisocyanate and its use for producing polyurethane foams |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101563387A true CN101563387A (en) | 2009-10-21 |
| CN101563387B CN101563387B (en) | 2012-02-01 |
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| CN200780042797XA Expired - Fee Related CN101563387B (en) | 2006-11-17 | 2007-11-12 | Polyphenylenepolymethylene polyisocyanate and its use for producing polyurethane foams |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20100076101A1 (en) |
| EP (1) | EP2091992A1 (en) |
| JP (1) | JP2010510339A (en) |
| KR (1) | KR20090091739A (en) |
| CN (1) | CN101563387B (en) |
| WO (1) | WO2008058920A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104080827A (en) * | 2012-01-18 | 2014-10-01 | 巴斯夫欧洲公司 | Method for producing rigid polyurethane foams |
| CN105764945A (en) * | 2013-12-04 | 2016-07-13 | 科思创德国股份有限公司 | Reaction system for a low-monomer one-component polyurethane foam |
| CN107531862A (en) * | 2015-04-21 | 2018-01-02 | 科思创德国股份有限公司 | The solid based on poly-isocyanurate polymer produced under adiabatic conditions |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DK2111423T3 (en) * | 2007-01-12 | 2010-11-08 | Basf Se | Rigid polyurethane foams |
| GB201106774D0 (en) * | 2011-04-21 | 2011-06-01 | Occutec Ltd | Polymers for contact lenses |
| US10472454B2 (en) | 2012-01-18 | 2019-11-12 | Basf Se | Preparing rigid polyurethane foams |
| US9758613B2 (en) * | 2012-04-30 | 2017-09-12 | Covestro Deutschland Ag | Method for producing foamed molded bodies |
| PL235304B1 (en) * | 2014-01-14 | 2020-06-29 | Selena Labs Spolka Z Ograniczona Odpowiedzialnoscia | Single-component mixture of isocyanate prepolymer for producing polyurethane product in a one-stage process |
| JP6480775B2 (en) * | 2015-03-26 | 2019-03-13 | 積水化学工業株式会社 | Urethane resin composition, fireproof reinforcing method for building material, and fireproof reinforcing structure for building material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4465639A (en) * | 1983-01-26 | 1984-08-14 | The Upjohn Company | Process for polyisocyanates |
| ZA883499B (en) * | 1987-05-26 | 1988-11-28 | ||
| JP3091080B2 (en) * | 1994-05-23 | 2000-09-25 | 三井化学株式会社 | Method for producing methylene-crosslinked polyphenylene polyisocyanate |
| SK170899A3 (en) * | 1997-06-13 | 2000-06-12 | Huntsman Ici Chemicals Llc The | Isocyanate compositions for blown polyurethane foams |
| EP1518874B1 (en) * | 2003-09-24 | 2006-12-13 | Basf Aktiengesellschaft | Polymeric MDI having low monomer content |
| CN101421326B (en) * | 2006-04-12 | 2011-10-26 | 巴斯夫欧洲公司 | Process for preparing polyurethanes |
| DK2111423T3 (en) * | 2007-01-12 | 2010-11-08 | Basf Se | Rigid polyurethane foams |
| US20090082481A1 (en) * | 2007-09-21 | 2009-03-26 | O'connor James | Preparation of liquid isocyanurate-modified polymethylene bis(phenylisocyanate) compositions of controlled viscosities |
| US20090105359A1 (en) * | 2007-09-21 | 2009-04-23 | O'connor James | Preparation of Liquid Isocyanurate-Modified Polymethylene Bis(Phenylisocyanate) Compositions of Controlled Viscosities |
-
2007
- 2007-11-12 US US12/513,515 patent/US20100076101A1/en not_active Abandoned
- 2007-11-12 CN CN200780042797XA patent/CN101563387B/en not_active Expired - Fee Related
- 2007-11-12 WO PCT/EP2007/062188 patent/WO2008058920A1/en active Application Filing
- 2007-11-12 KR KR1020097011536A patent/KR20090091739A/en not_active Application Discontinuation
- 2007-11-12 JP JP2009536712A patent/JP2010510339A/en not_active Withdrawn
- 2007-11-12 EP EP07822476A patent/EP2091992A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104080827A (en) * | 2012-01-18 | 2014-10-01 | 巴斯夫欧洲公司 | Method for producing rigid polyurethane foams |
| CN104080827B (en) * | 2012-01-18 | 2016-04-27 | 巴斯夫欧洲公司 | Prepare the method for hard polyurethane foams |
| CN105764945A (en) * | 2013-12-04 | 2016-07-13 | 科思创德国股份有限公司 | Reaction system for a low-monomer one-component polyurethane foam |
| CN107531862A (en) * | 2015-04-21 | 2018-01-02 | 科思创德国股份有限公司 | The solid based on poly-isocyanurate polymer produced under adiabatic conditions |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2091992A1 (en) | 2009-08-26 |
| KR20090091739A (en) | 2009-08-28 |
| CN101563387B (en) | 2012-02-01 |
| JP2010510339A (en) | 2010-04-02 |
| US20100076101A1 (en) | 2010-03-25 |
| WO2008058920A1 (en) | 2008-05-22 |
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